U.S. patent application number 17/110408 was filed with the patent office on 2021-06-03 for hard surface cleaning composition and method of improving surface shine using the same.
The applicant listed for this patent is The Procter & Gamble Company. Invention is credited to William Alexander CYNECKI, Brian Christopher GROENDYKE, Daniel Ross MAYFIELD, Fernando Ray TOLLENS, Pauline Cuc VU.
Application Number | 20210163854 17/110408 |
Document ID | / |
Family ID | 1000005291490 |
Filed Date | 2021-06-03 |
United States Patent
Application |
20210163854 |
Kind Code |
A1 |
TOLLENS; Fernando Ray ; et
al. |
June 3, 2021 |
HARD SURFACE CLEANING COMPOSITION AND METHOD OF IMPROVING SURFACE
SHINE USING THE SAME
Abstract
A hard surface cleaning composition, methods of cleaning a hard
surface with a low hysteresis composition and disposable
premoistened pads for cleaning hard surfaces are provided. The hard
surface cleaning composition includes from 0.01 wt. % to 7 wt. % of
a solvent selected from the group consisting of a propylene glycol
phenyl ether, a dipropylene glycol phenyl ethers and mixtures
thereof and at least 92% water. The cleaning composition has a pH
from about 3.5 to 9.5 and is free of anionic surfactant and
alkanolamine.
Inventors: |
TOLLENS; Fernando Ray;
(Cincinnati, OH) ; VU; Pauline Cuc; (FLORENCE,
KY) ; GROENDYKE; Brian Christopher; (NEWPORT, KY)
; CYNECKI; William Alexander; (MIDLAND, MI) ;
MAYFIELD; Daniel Ross; (SAGINAW, MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Procter & Gamble Company |
Cincinnati |
OH |
US |
|
|
Family ID: |
1000005291490 |
Appl. No.: |
17/110408 |
Filed: |
December 3, 2020 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
62942852 |
Dec 3, 2019 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11D 3/43 20130101; C11D
1/75 20130101; C11D 17/049 20130101; A47L 13/17 20130101; B08B
1/006 20130101; C11D 3/222 20130101; A47L 13/20 20130101; C11D 3/30
20130101; C11D 11/0023 20130101; B08B 3/08 20130101; C11D 3/201
20130101 |
International
Class: |
C11D 3/43 20060101
C11D003/43; C11D 3/30 20060101 C11D003/30; C11D 3/20 20060101
C11D003/20; C11D 3/22 20060101 C11D003/22; C11D 1/75 20060101
C11D001/75; C11D 17/04 20060101 C11D017/04; C11D 11/00 20060101
C11D011/00; B08B 1/00 20060101 B08B001/00; B08B 3/08 20060101
B08B003/08; A47L 13/17 20060101 A47L013/17; A47L 13/20 20060101
A47L013/20 |
Claims
1. A hard surface cleaning composition comprising: 0.01 wt. % to 7
wt. % of a solvent selected from the group consisting of a
propylene glycol phenyl ether, a dipropylene glycol phenyl ethers
and mixtures thereof and at least 92 wt. % water, wherein the
cleaning composition has a pH from about 3.5 to 9.5 and is free of
anionic surfactant and alkanolamine.
2. The composition according to claim 1, wherein the composition
further comprises from about 0.005 wt. % to about 0.5 wt. %
non-ionic surfactant.
3. The composition according to claim 1, wherein the composition
further comprises from about 0.005 wt % to 0.1 wt % of a quaternary
material.
4. The composition according to claim 1, wherein the quaternary
compound is selected from the group consisting of a C6-C18
alkyltrimethylammonium chloride, a C6-C18 dialkyldimethylammonium
chloride, and mixtures thereof.
5. The composition according to claim 1, wherein the solvent has an
HLB between 5.5 and 6.5 is present at a level of 0.2 wt. % to 1.5
wt. %, by weight of the overall composition.
6. The composition according to claim 1, wherein the composition
has a pH in the range of 3.5 to 9.5.
7. The composition according to claim 1, further comprising from
0.05% to 1 of a solubilizing aid by weight of the cleaning
composition; wherein the solubilizing aid is ethanol.
8. The composition according to claim 1, wherein the water is in an
amount from 97% to 99.5%, by weight of the cleaning
composition.
9. A method of improving shine of a hard surface, comprising the
steps of: a. wetting the hard surface with the cleaning composition
of claim 1 and b. removing the cleaning composition from the hard
surface with a disposable dry-cleaning wipe.
10. The method of claim 9, wherein the composition comprises less
than 0.5 wt. % ethanol.
11. The method of claim 9, wherein the solvent has an HLB between
6.5 and 7 and is present at a level of 0.2 wt. % to 1.0 wt. %, by
weight of the overall composition.
12. The method of claim 9, wherein the composition has a pH in the
range of 6 to 8.
13. The method of claim 9, wherein the composition further
comprises from about 0.01 wt % to about 0.08 wt % of a quaternary
compound selected from the group consisting of a C6-C18
alkyltrimethylammonium chloride, a C6-C18dialkyldimethylammonium
chloride, and mixtures thereof.
14. A disposable premoistened pad for cleaning hard surfaces
comprising: a substrate and a liquid hard surface cleaning
composition according to claim 1, wherein said substrate is
impregnated with said cleaning composition.
15. The disposable premoistened pad of claim 14, wherein the pad
comprises cellulose and an antibacterial material, wherein the
cellulose content of the substrate as basis weight between 80 to
148 gsm and expresses the antibacterial material between 200 to 600
ppm.
16. The disposable premoistened pad of claim 14, wherein the pad
comprises cellulose and an antibacterial material, wherein the
cellulose content of the pad as basis weight between 80 to 148
gsm.
17. The disposable premoistened pad of claim 14, wherein the
substrate comprises cellulose and an antibacterial material,
wherein the pad expresses the antibacterial material between 200 to
600 ppm.
18. A cleaning implement comprising: a handle; a plastic head; a
cleaning pad removably connectable with the plastic head; a
reservoir connected with or separated from the handle; and a liquid
hard surface cleaning composition according to claim 1, wherein the
cleaning pad is impregnated with the cleaning composition.
Description
FIELD
[0001] The present disclosure is generally directed to a hard
surface cleaning composition and methods of improving surface shine
and reducing streaks and water marks of a cleaning composition
using the dewetting behaviour of low hydrophile-lipophile balance
solvents; also known as hysteresis.
BACKGROUND
[0002] Hard surface cleaning compositions are used for cleaning and
treating hard surfaces. Preferably, the hard surface cleaning
composition is formulated to be an "all purpose" hard surface
cleaning composition. That is, the hard surface cleaning
composition is formulated to be suitable for cleaning as many
different kinds of surfaces as possible. However, it historically
has been challenging to formulate a hard surface cleaning
composition which effectively cleans tiles, and more delicate
surfaces such as wood, stainless steel, linoleum, marble, and the
like. When cleaning particularly dirty floors, film and streak
residues or water marks may be left behind which result in low
shine, and an impression that the surface is not yet sufficiently
clean. In addition, such floors, washed with diluted hard surface
cleaning compositions tend to be slippery with a resultant increase
in the risk of falls and similar accidents. As a result, the floor
is sometimes rinsed again using fresh water, to remove such films
and streaks or water marks in order to improve the impression of
cleanliness.
[0003] Hence, a need remains for a composition which provides
improved shine and reduced streaks and water marks, even after
cleaning especially dirty floors.
SUMMARY
[0004] Aspects of the present disclosure include a hard surface
cleaning composition that includes from 0.01 wt. % to 7 wt. % of a
solvent selected from the group consisting of a propylene glycol
phenyl ether, a dipropylene glycol phenyl ethers and mixtures
thereof and at least 92% water. The cleaning composition has a pH
from about 3.5 to 9.5 and is free of anionic surfactant and
alkanolamine
[0005] Aspects of the present disclosure also include a methods of
cleaning a hard surfaces with reduced film and streak residues or
water marks, the method comprising the steps of: wetting the hard
surface with a cleaning composition, and removing the cleaning
composition from the hard surface with a disposable dry cleaning
wipe. The hard surface cleaning composition includes from 0.01 wt.
% to 7 wt. % of a solvent selected from the group consisting of a
propylene glycol phenyl ether, a dipropylene glycol phenyl ethers
and mixtures thereof and at least 92% water. The cleaning
composition has a pH from about 3.5 to 9.5 and is free of anionic
surfactant and alkanolamine.
[0006] Aspects of the present disclosure also include disposable
premoistened pads for cleaning hard surfaces that include a
substrate and a liquid hard surface cleaning composition. The
substrate is impregnated with the cleaning composition. The
cleaning composition includes from 0.01 wt. % to 7 wt. % of a
solvent selected from the group consisting of a propylene glycol
phenyl ether, a dipropylene glycol phenyl ethers and mixtures
thereof and at least 92% water. The cleaning composition has a pH
from about 3.5 to 9.5 and is free of anionic surfactant and
alkanolamine.
[0007] Aspects of the present disclosure also include cleaning
implements that include a handle, a plastic head, a cleaning pad
removably connectable with the plastic head, a reservoir connected
with or separated from the handle; and a liquid hard surface
cleaning composition. The cleaning composition includes from 0.01
wt. % to 7 wt. % of a solvent selected from the group consisting of
a propylene glycol phenyl ether, a dipropylene glycol phenyl ethers
and mixtures thereof and at least 92% water. The cleaning
composition has a pH from about 3.5 to 9.5 and is free of anionic
surfactant and alkanolamine.
DETAILED DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1A is a top perspective view an exemplary cleaning pad
according to the present invention shown partially in cutaway.
[0009] FIG. 1B is a bottom plan view of the cleaning pad of FIG.
1A, shown partially in cutaway and having one attachment strip
truncated for clarity.
[0010] FIG. 2 is a schematic, vertical sectional view taken along
lines 2-2 of FIG. 1B.
[0011] FIG. 3 is a perspective view of a cleaning implement usable
with the cleaning pad of the present invention and showing the
cleaning pad in position to be removably attached to the cleaning
implement.
[0012] FIG. 4 is a illustrates the processes pinning and
dewetting.
DETAILED DESCRIPTION
[0013] As defined herein, "essentially free of" a component means
that no amount of that component is deliberately incorporated into
the respective premix, or composition. Preferably, "essentially
free of" a component means that no amount of that component is
present in the respective premix, or composition, but may be
present as trace impurities.
[0014] As used herein, "isotropic" means a clear mixture, having
little or no visible haziness, phase separation and/or dispersed
particles, and having a uniform transparent appearance.
[0015] As defined herein, "stable" means that no visible phase
separation is observed for a premix kept at 25.degree. C. for a
period of at least two weeks, or at least four weeks, or greater
than a month or greater than four months, as measured using the
Floc Formation Test, described in USPA 2008/0263780 A1.
[0016] By "Low volatile organic compound hard surface cleaning
composition", it is meant herein a finished product having low
volatile organic compound ("VOC") content like, for example, a
maximum of 0.5% by weight of the composition of VOCs, however, it
is noted that fragrance is exempted from this value up to 2% by the
weight of the finished product.
[0017] All percentages, ratios and proportions used herein are by
weight percent of the premix, unless otherwise specified. All
average values are calculated "by weight" of the premix, unless
otherwise expressly indicated.
[0018] All measurements are performed at 25.degree. C. unless
otherwise specified.
[0019] Unless otherwise noted, all component or composition levels
are in reference to the active portion of that component or
composition, and are exclusive of impurities, for example, residual
solvents or by-products, which may be present in commercially
available sources of such components or compositions.
[0020] Liquid Hard Surface Cleaning Compositions
[0021] By "liquid hard surface cleaning composition", it is meant
herein a liquid composition for cleaning hard surfaces found in
households, especially domestic households. Surfaces to be cleaned
include kitchens and bathrooms, e.g., floors, walls, tiles,
windows, cupboards, sinks, showers, shower plastified curtains,
wash basins, WCs, fixtures and fittings and the like made of
different materials like ceramic, vinyl, no-wax vinyl, linoleum,
melamine, glass, steel, kitchen work surfaces, any plastics, wood,
plastified wood, metal or any painted or varnished or sealed
surface and the like. Household hard surfaces also include
household appliances including, but not limited to refrigerators,
freezers, washing machines, automatic dryers, ovens, microwave
ovens, dishwashers and so on. Such hard surfaces may be found both
in private households as well as in commercial, institutional and
industrial environments.
[0022] In a preferred embodiment, the liquid compositions herein
are aqueous compositions. Therefore, they may comprise from 92% to
99.7% by weight of the total composition of water, preferably at
least about 93 wt %, more preferably at least about 95 wt %, more
preferably at least about 97 wt %, most preferably at least about
98 wt % water.
[0023] The compositions of the present disclosure preferably have a
viscosity from lcps to 650 cps, more preferably of from 100 cps to
550 cps, more preferably from 150 cps to 450 cps, most preferably
from 250 cps to 350 cps when measured at 20.degree. C. with a
AD1000 Advanced Rheometer from Atlas.RTM. shear rate 10 s-1 with a
coned spindle of 40 mm with a cone angle 2.degree. and a truncation
of .+-.60 .mu.m.
[0024] The pH is preferably from 3.5 to 9.5, more preferably from 5
to 8 and most preferably from 6 to 7.
[0025] It will be understood that the compositions herein may
further comprise an acid or base to adjust pH as appropriate.
[0026] A suitable acid for use herein is an organic and/or an
inorganic acid. A preferred organic acid for use herein has a pKa
of less than 7. A suitable organic acid is selected from the group
consisting of: citric acid, lactic acid, glycolic acid, maleic
acid, malic acid, succinic acid, glutaric acid and adipic acid and
mixtures thereof. A suitable inorganic acid can be selected from
the group consisting of: hydrochloric acid, sulphuric acid,
phosphoric acid and mixtures thereof.
[0027] A typical level of such acids, when present, is from 0.001%
to 1.0% by weight of the total composition, preferably from 0.005%
to 0.5% and more preferably from 0.01% to 0.05%.
[0028] A suitable base to be used herein is an organic and/or
inorganic base. Suitable bases for use herein are the caustic
alkalis, such as sodium hydroxide, potassium hydroxide and/or
lithium hydroxide, and/or the alkali metal oxides such, as sodium
and/or potassium oxide or mixtures thereof. A preferred base is a
caustic alkali, more preferably sodium hydroxide and/or potassium
hydroxide.
[0029] Other suitable bases include ammonia, ammonium carbonate,
K.sub.2CO.sub.3, Na.sub.2CO.sub.3 and alkanolamines (such as
monoethanolamine, triethanolamine, aminomethylpropanol, and
mixtures thereof).
[0030] Typical levels of such bases, when present, are from 0.001%
to 1.0% by weight of the total composition, preferably from 0.005%
to 0.5% and more preferably from 0.01% to 0.05%.
[0031] Solvent
[0032] The liquid hard surface cleaning compositions preferably
comprises a propylene phenyl glycol esthers solvent. The solvent
comprises a propylene glycol phenyl ether or dipropylene glycol
phenyl ethers solvent and a combination thereof with an HLB value
of 5.5 to 6.5.
[0033] It was found that a composition having a propylene phenyl
glycol esthers solvent with an HLB value of 5.5 to 6.5 delivered
good cleaning with an unexpectedly low streaks and water marks as
compared to compositions with traditional solvent systems.
[0034] Without being bound by theory, a composition having a
solvent or solvents with the preferred HLB value for example,
propylene glycol phenyl ether or dipropylene glycol phenyl ethers
solvent, provides sufficient water solubility for solution
stability and enough oil compatibility for oil or lipid solubility.
Propylene glycol phenyl ether and dipropylene glycol phenyl ethers
solvents or solvents deliver optimum oil solubility for cleaning,
soil dissolution, and absorption while maintaining a low level of
streaks and water marks coming from their ability to dewett during
the drying process.
[0035] A phenyl glycol ether having an HLB between 5.5 and 6.5 may
be selected from the group consisting of: propylene glycol phenyl
ether and dipropylene glycol phenyl ether, and combinations
thereof. Exemplary glycol ethers having an HLB between 5.5 and 6.5
are DOWANOL.TM. PPH, DOWANOL.TM. DiPPH Glycol Ether, and
DOWANOL.TM. CNTR from the Dow Chemical Company.
[0036] The phenyl glycol ether solvent may be present at a level of
0.05 wt. % to 3.50 wt. %, more preferably 0.1 wt. % to 1.5 wt. %,
most preferably 0.3 wt. % to 0.9 wt. %, by weight of the overall
composition.
[0037] The composition may comprise less than 0.5 wt. % ethanol,
more preferably less than 0.4 wt. % ethanol, and most preferably
less than 0.3 wt. % ethanol. Without wishing to be bound by theory,
it is believed that higher levels of ethanol negatively impacting
the hysteresis of the composition and increase the streaking of the
composition on the hard surface.
[0038] During the cleaning process, surfaces may undergo four
transformations, cycles or stages: application of the solution to
wet the surface, wetting and spreading of the solution on the
surface, optional removal of the solution from the surface that can
include absorption into a cleaning substrate, and drying of any
residual solution which on horizontals surfaces, like floors,
occurs mainly by evaporation. However, during the drying cycle the
wetting and spreading characteristics of the solution, which are
controlled by the interaction between fluid and the surface
interface, are important for the final appearance of the cleaning
surface. The effect of the wetting behavior of the solution during
the drying cycle is a phenomenal that is not well understood.
During the drying cycle the solution evaporates forming beads and
depending on their chemical composition these beads would evaporate
by pining or dewetting. As shown in FIG. 4, these two phenomena,
pinning or dewetting, can significantly impact spotting and/or
streaking of the solution left behind. When a solution evaporates
through a pinning process, the area and the radius of the bead
contacting the surface remains constant while the volume and the
contact angle between the fluid and the surface decreases. This
results in streaks and/or water marks of the size of the area or
radius of the original bead which has a negative impact in cleaning
appearance and shine. On the other hand, when a solution evaporates
through a dewetting process, the area, the radius of the bead
contacting the surface, and its volume decreases while the contact
angle between the fluid and the surface remains contact. This
results in the reduction of the area and radius of the original
bead which reduces its foot print on the surface as the beads
evaporate resulting in smaller and less visible streaks and water
marks. One parameter that is important for the dewetting behaviour
of the solution is its degree of hysterisis, which is defined as
the substraction of its advancing contact minus its receiding
contact angle. The hysterisis of the solution controls how the
solution wets or spread and dewetts or recede on the surface. This
hysterisis is a dynamic process with its advancing component
controlling wetting, for example during the wetting cycle; and its
receding component controlling dewetting during the drying process.
High hysteresis solutions, or solutions with higher advancing
contact angle component, have a higher tendency to spread and are
less prone to dewett. While low hysteresis solutions, or solutions
with lower advancing contact angle or higher receding contact angle
component, have a higher tendency to recede and are more prone to
deweet. It has been found that solutions containing high
hydrophobic solvents with a Hydrophile-Lipophile Balance between
5.5 to 6.5, such as phenyl glycol ethers, more specifically
propylene phenyl glycol ethers results in low hysteresis less than
30.degree., more preferably less than 20.degree., and most
preferably less than 10.degree. offer dewetting benefits. Without
being bound by theory, it is believed that optimum dewetting and
shine results are found with a solutions preferably having a
hysteresis than lower than 30.degree., more preferably lower than
20.degree., and most preferably lower than 10.degree.. This benefit
is of particular importance in cleaning application without a rinse
or that are not completely absorbed during the cleaning
process.
[0039] The benefit of these solvents can also show benefits when
the composition comprises an antibacterial (as discussed further
herein), such as a quaternary ammonium. Specifically, antibacterial
compositions, such as those with quaternary ammonium are known to
be poor dewetters and tend to cause stickiness problems if used at
high concentration or if left behind on the cleaning surface. The
benefit with antibacterial formulations can be further improved
when the pad or wipe contains airlaid cellulose because, without
being bound by theory, the negative charge sites in the cellulose
bind to the quaternary ammonium and reduce their free or expressed
concentration that can reach the cleaning surface reducing their
negative impact in cleaning while still delivering high micro
efficacy.
[0040] Non-Ionic Surfactant
[0041] The liquid hard surface cleaning composition of the present
disclosure may include an amine oxide surfactant a non-ionic
surfactant. The non-ionic surfactant may be present at a level of
0.005 wt. % to 0.5 wt. %, more preferably 0.01 wt. % to 0.1 wt. %,
most preferably 0.04 wt. % to 0.06 wt. %, by weight of the overall
composition.
[0042] Suitable non-ionic surfactants include amine oxide
surfactants which include: R1R2R3NO wherein each of R.sub.1,
R.sub.2 and R.sub.3 is independently a saturated or unsaturated,
substituted or unsubstituted, linear or branched hydrocarbon chain
having from 10 to 30 carbon atoms. Preferred amine oxide
surfactants are amine oxides having the following formula:
R.sub.1R.sub.2R.sub.3NO wherein R.sub.1 is an hydrocarbon chain
comprising from 1 to 30 carbon atoms, preferably from 6 to 20, more
preferably from 8 to 16 and wherein R.sub.2 and R.sub.3 are
independently saturated or unsaturated, substituted or
unsubstituted, linear or branched hydrocarbon chains comprising
from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and
more preferably are methyl groups. R.sub.1 may be a saturated or
unsaturated, substituted or unsubstituted linear or branched
hydrocarbon chain.
[0043] A highly preferred amine oxide is C.sub.12-C.sub.14 dimethyl
amine oxide, commercially available from Albright & Wilson,
C.sub.12-C.sub.14 amine oxides commercially available under the
trade name Genaminox.RTM. LA from Clariant or AROMOX.RTM. DMC from
AKZO Nobel.
[0044] Another suitable non-ionic surfactants are ethoxylated
alkoxylated nonionic surfactant. The ethoxylated alkoxylated
nonionic surfactant is preferably selected from the group
consisting of: esterified alkyl alkoxylated surfactant; alkyl
ethoxy alkoxy alcohol, wherein the alkoxy part of the molecule is
preferably propoxy, or butoxy, or propoxy-butoxy; polyoxyalkylene
block copolymers, and mixtures thereof.
[0045] The preferred ethoxylated alkoxylated nonionic surfactant is
an esterified alkyl alkoxylated surfactant of general formula
(I):
##STR00001##
where
[0046] R is a branched or unbranched alkyl radical having 8 to 16
carbon atoms, preferably from 10 to 16 and more preferably from 12
to 15;
[0047] R3, R1 independently of one another, are hydrogen or a
branched or unbranched alkyl radical having 1 to 5 carbon atoms;
preferably R3 and R1 are hydrogen
[0048] R2 is an unbranched alkyl radical having 5 to 17 carbon
atoms; preferably from 6 to 14 carbon atoms
[0049] l, n independently of one another, are a number from 1 to 5
and
[0050] m is a number from 8 to 50; and
[0051] Preferably, the weight average molecular weight of the
ethoxylated alkoxylated nonionic surfactant of formula (I) is from
950 to 2300 g/mol, more preferably from 1200 to 1900 g/mol.
[0052] R is preferably from 12 to 15, preferably 13 carbon atoms.
R3 and R1 are preferably hydrogen. Component l is preferably 5. n
is preferably 1. m is preferably from 13 to 35, more preferably 15
to 25, most preferably 22. R2 is preferably from 6 to 14 carbon
atoms.
[0053] The hard surface cleaning composition of the invention
provides especially high shine when the esterified alkyl akoxylated
surfactant is as follows: R has from 12 to 15, preferably 13 carbon
atoms, R3 is hydrogen, R1 is hydrogen, component l is 5, n is 1, m
is from 15 to 25, preferably 22 and R2 has from 6 to 14 carbon
atoms and the alcohol ethoxylated has an aliphatic alcohol chain
containing from 10 to 14, more preferably 13 carbon atoms and from
5 to 8, more preferably 7 molecules of ethylene oxide.
[0054] Preferably, the ethoxylated alkoxylated nonionic surfactant
can be a polyoxyalkylene copolymer. The polyoxyalkylene copolymer
can be a block-heteric ethoxylated alkoxylated nonionic surfactant,
though block-block surfactants are preferred. Suitable
polyoxyalkylene block copolymers include ethylene oxide/propylene
oxide block polymers, of formula (II):
(EO)x(PO)y(EO)x, or (II)
(PO)x(EO)y(PO)x (II)
wherein EO represents an ethylene oxide unit, PO represents a
propylene oxide unit, and x and y are numbers detailing the average
number of moles ethylene oxide and propylene oxide in each mole of
product. Such materials tend to have higher molecular weights than
most non-ionic surfactants, and as such can range between 1000 and
30000 g/mol, although the molecular weight should be above 2200 and
preferably below 13000. A preferred range for the molecular weight
of the polymeric non-ionic surfactant is from 2400 to 11500
Daltons. BASF (Mount Olive, N.J.) manufactures a suitable set of
derivatives and markets them under the Pluronic trademarks.
Examples of these are Pluronic (trademark) F77, L62 and F88 which
have the molecular weight of 6600, 2450 and 11400 g/mol
respectively. An especially preferred example of a useful polymeric
non-ionic surfactant is Pluronic (trademark) F77.
[0055] Other suitable ethoxylated alkoxylated nonionic surfactants
are described in Chapter 7 of Surfactant Science and Technology,
Third Edition, Wiley Press, ISBN 978-0-471-68024-6.
[0056] The ethoxylated alkoxylated nonionic surfactant preferably
provides a wetting effect of from 15 to 350 s, more preferably from
60 to 200 s, even more preferably from 75 to 150 s. The wetting
effect is measured according to EN 1772, using 1 g/l of the
ethoxylated alkoxylated nonionic surfactant in distilled water, at
23.degree. C., with 2 g soda/l.
[0057] The ethoxylated alkoxylated nonionic surfactants preferably
are low foaming non-ionic surfactants that are alkoxylated and
include unbranched fatty alcohols that may contain high amounts of
alkene oxide and ethylene oxide. For example, preferred ethoxylated
alkoxylated nonionic surfactants may include those sold by BASF
under the "Plurafac" trademark, especially Plurafac LF 131 (wetting
effect of 25 s), LF 132 (wetting effect of 70 s), LF 231 (wetting
effect of 40 s), LF 431 (wetting effect of 30 s), LF 1530 (wetting
effect>300 s), LF 731 (wetting effect of 100 s), LF 1430
(wetting effect>300 s) and LF 7319 (wetting effect of 100
s).
[0058] The ethoxylated alkoxylated nonionic surfactants preferably
are not hydrogenated and, therefore, the fatty alcohol chains do
not terminate in a hydrogen group. Examples of such hydrogenated
non-ionic surfactants include Plurafac 305 and Plurafac 204.
[0059] Another suitable non-ionic surfactants are alkoxylated
nonionic surfactants, alkyl polyglycosides, and mixture
thereof.
[0060] Suitable alkoxylated nonionic surfactants include primary
C.sub.6-C.sub.16 alcohol polyglycol ether i.e. ethoxylated alcohols
having 6 to 16 carbon atoms in the alkyl moiety and 4 to 30
ethylene oxide (EO) units. When referred to for example C.sub.9-14
it is meant average carbons and alternative reference to for
example EO8 is meant average ethylene oxide units.
[0061] Suitable alkoxylated nonionic surfactants are according to
the formula RO-(A).sub.nH, wherein: R is a C.sub.6 to C.sub.18,
preferably a C.sub.8 to C.sub.16, more preferably a C.sub.8 to
C.sub.12 alkyl chain, or a C.sub.6 to C.sub.28 alkyl benzene chain;
A is an ethoxy or propoxy or butoxy unit, and wherein n is from 1
to 30, preferably from 1 to 15 and, more preferably from 4 to 12
even more preferably from 5 to 10. Preferred R chains for use
herein are the C.sub.8 to C.sub.22 alkyl chains. Even more
preferred R chains for use herein are the C.sub.9 to C.sub.12 alkyl
chains. R can be linear or branched alkyl chain.
[0062] Suitable ethoxylated nonionic surfactants for use herein are
Dobanol.RTM. 91-2.5 (HLB=8.1; R is a mixture of C.sub.9 and
C.sub.11 alkyl chains, n is 2.5), Dobanol.RTM. 91-10 (HLB=14.2; R
is a mixture of C.sub.9 to C.sub.11 alkyl chains, n is 10),
Dobanol.RTM. 91-12 (HLB=14.5 ; R is a mixture of C.sub.9 to
C.sub.11 alkyl chains, n is 12), Greenbentine DE80 (HLB=13.8, 98 wt
% C10 linear alkyl chain, n is 8), Marlipal 10-8 (HLB=13.8, R is a
C10 linear alkyl chain, n is 8), Lialethl.RTM. 11-5 (R is a
C.sub.11 alkyl chain, n is 5), Isalchem.RTM. 11-5 (R is a mixture
of linear and branched C11 alkyl chain, n is 5), Lialethl.RTM.
11-21 (R is a mixture of linear and branched C.sub.11 alkyl chain,
n is 21), Isalchem.RTM. 11-21 (R is a C.sub.11 branched alkyl
chain, n is 21), Empilan.RTM. KBE21 (R is a mixture of C.sub.12 and
C.sub.14 alkyl chains, n is 21) or mixtures thereof. Preferred
herein are Dobanol.RTM. 91-5, Neodol.RTM. 11-5, Lialethl.RTM. 11-21
Lialethl.RTM. 11-5 Isalchem.RTM. 11-5 Isalchem.RTM. 11-21
Dobanol.RTM. 91-8, or Dobanol.RTM. 91-10, or Dobanol.RTM. 91-12, or
mixtures thereof. These Dobanol.RTM./Neodol.RTM. surfactants are
commercially available from SHELL. These Lutensol.RTM. surfactants
are commercially available from BASF and these Tergitol.RTM.
surfactants are commercially available from Dow Chemicals.
[0063] Suitable chemical processes for preparing the alkoxylated
nonionic surfactants for use herein include condensation of
corresponding alcohols with alkylene oxide, in the desired
proportions. Such processes are well known to the person skilled in
the art and have been extensively described in the art, including
the OXO process and various derivatives thereof. Suitable
alkoxylated fatty alcohol nonionic surfactants, produced using the
OXO process, have been marketed under the tradename NEODOL.RTM. by
the Shell Chemical Company. Alternatively, suitable alkoxylated
nonionic surfactants can be prepared by other processes such as the
Ziegler process, in addition to derivatives of the OXO or Ziegler
processes.
[0064] Preferably, said alkoxylated nonionic surfactant is a
C.sub.9-11 EO5 alkylethoxylate, C.sub.12-14 EO5 alkylethoxylate, a
C.sub.11 EO5 alkylethoxylate, C.sub.12-14 EO21 alkylethoxylate, or
a C.sub.9-11 EO8 alkylethoxylate or a mixture thereof. Most
preferably, said alkoxylated nonionic surfactant is a C.sub.11 EO5
alkylethoxylate or a C.sub.9-11 EO8 alkylethoxylate or a mixture
thereof.
[0065] Another suitable non-ionic surfactants are Alkyl
polyglycosides, which are biodegradable nonionic surfactants which
are well known in the art. Suitable alkyl polyglycosides can have
the general formula
C.sub.nH.sub.2n+1O(C.sub.6H.sub.10O.sub.5).sub.xH wherein n is
preferably from 9 to 16, more preferably 11 to 14, and x is
preferably from 1 to 2, more preferably 1.3 to 1.6. Such alkyl
polyglycosides provide a good balance between anti-foam activity
and detergency. Alkyl polyglycoside surfactants are commercially
available in a large variety. An example of a very suitable alkyl
poly glycoside product is Planteren APG 600, which is essentially
an aqueous dispersion of alkyl polyglycosides wherein n is about 13
and x is about 1.4.
[0066] The additional nonionic surfactant is preferably a low
molecular weight nonionic surfactant, having a molecular weight of
less than 950 g/mol, more preferably less than 500 g/mol.
[0067] Another suitable non-ionic surfactants are suitable
zwitterionic surfactants. Zwitterionic surfactants typically
contain both cationic and anionic groups in substantially
equivalent proportions so as to be electrically neutral at the pH
of use. The typical cationic group is a quaternary ammonium group,
other positively charged groups like phosphonium, imidazolium and
sulfonium groups can be used. The typical anionic hydrophilic
groups are carboxylates and sulfonates, although other groups like
sulfates, phosphonates, and the like can be used.
[0068] Some common examples of zwitterionic surfactants (such as
betaine/sulphobetaine surfacants) are described in U.S. Pat. Nos.
2,082,275, 2,702,279 and 2,255,082. For example Coconut dimethyl
betaine is commercially available from Seppic under the trade name
of Amonyl 265.RTM.. Lauryl betaine is commercially available from
Albright & Wilson under the trade name Empigen BB/L.RTM.. A
further example of betaine is Lauryl-imminodipropionate
commercially available from Rhodia under the trade name Mirataine
H2C-HA.RTM..
[0069] Sulfobetaine surfactants are particularly preferred, since
they can improve soap scum cleaning. Examples of suitable
sulfobetaine surfactants include tallow bis(hydroxyethyl)
sulphobetaine, cocoamido propyl hydroxy sulphobetaines which are
commercially available from Rhodia and Witco, under the trade name
of Mirataine CBS.RTM. and ReWoteric AM CAS 15.RTM.
respectively.
[0070] Another suitable non-ionic surfactants are amphoteric
surfactants. Amphoteric surfactants can be either cationic or
anionic depending upon the pH of the composition. Suitable
amphoteric surfactants include dodecylbeta-alanine, N-alkyltaurines
such as the one prepared by reacting dodecylamine with sodium
isethionate, as taught in U.S. Pat. No. 2,658,072, N-higher
alkylaspartic acids such as those taught in U.S. Pat. No.
2,438,091, and the products sold under the trade name "Miranol", as
described in U.S. Pat. No. 2,528,378. Other suitable additional
surfactants can be found in McCutcheon's Detergents and Emulsifers,
North American Ed. 1980.
[0071] Copolymer:
[0072] The cleaning composition may comprise from 0.005% to 1.5%,
more preferably from 0.01% to 1%, yet more preferably from 0.01% to
5%, most preferably from 0.01 to 0.06% by weight of the cleaning
composition, of a copolymer that comprises monomers selected from
the group comprising monomers of formula (III) (Monomer A) and
monomers of formula (IVa-IVd) (Monomer B) (hereinafter referred to
as "the copolymer"). The copolymer comprises from 60 to 99%,
preferably from 70 to 95% and especially from 80 to 90% by weight
of at least one monoethylenically unsaturated polyalkylene oxide
monomer of the formula (III) (monomer A)
##STR00002##
wherein Y of formula (III) is selected from --O-- and --NH--; if Y
of formula (III) is --O--, X of formula (III) is selected from
--CH.sub.2-- or --CO--, if Y of formula (III) is --NH--, X of
formula (III) is --CO--; R.sup.1 of formula (III) is selected from
hydrogen, methyl, and mixtures thereof; R.sup.2 of formula (III) is
independently selected from linear or branched
C.sub.2-C.sub.6-alkylene radicals, which may be arranged blockwise
or randomly; R.sup.3 of formula (III) is selected from hydrogen,
C.sub.1-C.sub.4-alkyl, and mixtures thereof; n of formula (III) is
an integer from 5 to 100, preferably from 10 to 70 and more
preferably from 20 to 50.
[0073] The copolymer comprises from 1 to 40%, preferably from 2 to
30% and especially from 5 to 20% by weight of at least one
quaternized nitrogen-containing monoethylenically unsaturated
monomer of formula (IVa-IVd) (monomer B).
[0074] The monomers are selected such that the copolymer has a
weight average molecular weight (Mw) of from 5,000 to 500,000
g/mol, preferably from greater than 7,000 to 150,000 g/mol and
especially from 10,000 to 80,000 g/mol.
[0075] The copolymer preferably has a net positive charge at a pH
of 3 or above.
[0076] The copolymer for use in the present disclosure may further
comprise monomers C and/or D. Monomer C may comprise from 0% to
15%, preferably from 0 to 10% and especially from 1 to 7% by weight
of the copolymer of an anionic monoethylenically unsaturated
monomer.
[0077] Monomer D may comprise from 0% to 40%, preferably from 1 to
30% and especially from 5 to 20% by weight of the copolymer of
other non-ionic monoethylenically unsaturated monomers.
[0078] Preferred copolymers according to the present disclosure
comprise, as copolymerized Monomer A, monoethylenically unsaturated
polyalkylene oxide monomers of formula (III) in which Y of formula
(III) is --O--; X of formula (III) is --CO--; R.sup.1 of formula
(III) is hydrogen or methyl; R.sup.2 of formula (III) is
independently selected from linear or branched
C.sub.2-C.sub.4-alkylene radicals arranged blockwise or randomly,
preferably ethylene, 1,2- or 1,3-propylene or mixtures thereof,
particularly preferably ethylene; R.sup.3 of formula (III) is
methyl; and n is an integer from 20 to 50.
[0079] Monomer A
[0080] A monomer A for use in the copolymer of the present
disclosure may be, for example: [0081] (a) reaction products of
(meth)acrylic acid with polyalkylene glycols which are not
terminally capped, terminally capped at one end by alkyl radicals;
and [0082] (b) alkenyl ethers of polyalkylene glycols which are not
terminally capped or terminally capped at one end by alkyl
radicals.
[0083] Preferred monomer A is the (meth)acrylates and the allyl
ethers, where the acrylates and primarily the methacrylates are
particularly preferred. Particularly suitable examples of the
monomer A are: [0084] (a) methylpolyethylene glycol (meth)acrylate
and (meth)acrylamide, methylpolypropylene glycol (meth)acrylate and
(meth)acrylamide, methylpolybutylene glycol (meth)acrylate and
(meth)acrylamide, methylpoly(propylene oxide-co-ethylene oxide)
(meth)acrylate and (meth)acrylamide, ethylpolyethylene glycol
(meth)acrylate and (meth)acrylamide, ethylpolypropylene glycol
(meth)acrylate and (meth)acrylamide, ethylpolybutylene glycol
(meth)acrylate and (meth)acrylamide and ethylpoly(propylene
oxide-co-ethylene oxide) (meth)acrylate and (meth)acrylamide, each
with 5 to 100, preferably 10 to 70 and particularly preferably 20
to 50, alkylene oxide units, where methylpolyethylene glycol
acrylate is preferred and methylpolyethylene glycol methacrylate is
particularly preferred; [0085] (b) ethylene glycol allyl ethers and
methylethylene glycol allyl ethers, propylene glycol allyl ethers
and methylpropylene glycol allyl ethers each with 5 to 100,
preferably 10 to 70 and particularly preferably 20 to 50, alkylene
oxide units.
[0086] The proportion of Monomer A in the copolymer according to
the present disclosure is 60% to 99% by weight, preferably 70% to
95%, more preferably from 80% to 90% by weight of the
copolymer.
[0087] Monomer B
[0088] A monomer B that is particularly suitable for the copolymer
of the present disclosure includes the quaternization products of
1-vinylimidazoles, of vinylpyridines, of (meth)acrylic esters with
amino alcohols, in particular
N,N-di-C.sub.1-C.sub.4-alkylamino-C.sub.2-C.sub.6-alcohols, of
amino-containing (meth)acrylamides, in particular
N,N-di-C.sub.1-C.sub.4-alkyl-amino-C.sub.2-C.sub.6-alkylamides of
(meth)acrylic acid, and of diallylalkylamines, in particular
diallyl-C.sub.1-C.sub.4-alkylamines.
[0089] Suitable monomers B have the formula IVa to IVd:
##STR00003##
wherein R of formula IVa to IVd is selected from
C.sub.1-C.sub.4-alkyl or benzyl, preferably methyl, ethyl or
benzyl; R' of formula IVc is selected from hydrogen or methyl; Y of
formula IVc is selected from --O-- or --NH--; A of formula IVc is
selected from C.sub.1-C.sub.6-alkylene, preferably straight-chain
or branched C.sub.2-C.sub.4-alkylene, in particular 1,2-ethylene,
1,3- and 1,2-propylene or 1,4-butylene; X-- of formula IVa to IVd
is selected from halide, such as iodide and preferably chloride or
bromide, C.sub.1-C.sub.4-alkyl sulfate, preferably methyl sulfate
or ethyl sulfate, C.sub.1-C.sub.4-alkylsulfonate, preferably
methylsulfonate or ethylsulfonate, C.sub.1-C.sub.4-alkyl carbonate;
and mixtures thereof.
[0090] Specific examples of preferred monomer B that may be
utilized in the present disclosure are: [0091] (a)
3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium
methyl sulfate, 3-ethyl-1-vinylimidazolium ethyl sulfate,
3-ethyl-1-vinylimidazolium chloride and 3-benzyl-1-vinylimidazolium
chloride; [0092] (b) 1-methyl-4-vinylpyridinium chloride,
1-methyl-4-vinylpyridinium methyl sulfate and
1-benzyl-4-vinylpyridinium chloride; [0093] (c)
3-methacrylamido-N,N,N-trimethylpropan-1-aminium chloride,
3-acryl-N,N,N-trimethylpropan-1-aminium chloride, 3-acryl
-N,N,N-trimethylpropan-1-aminium methyl sulfate,
3-methacryl-N,N,N-trimethylpropan-1-aminium chloride,
3-methacryl-N,N,N-trimethylpropan-1-aminium methyl sulfate, 2-acryl
amido-N,N,N-trimethylethan-1-aminium chloride,
2-acryl-N,N,N-trimethylethan-1-aminium chloride,
2-acryl-N,N,N-trimethylethan-1-aminium methyl sulfate,
2-methacryl-N,N,N-trimethylethan-1-aminium chloride,
2-methacryl-N,N,N-trimethylethan-1-aminium methyl sulfate,
2-acryl-N,N-dimethyl-N-ethylethan-1-aminium ethyl sulfate,
2-methacryl-N,N-dimethyl-N-ethylethan-1-aminium ethyl sulfate, and
[0094] (d) dimethyldiallylammonium chloride and
diethyldiallylammonium chloride.
[0095] A preferred monomer B is selected from
3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium
methyl sulfate, 3-methacryl-N,N,N-trimethylpropan-1-aminium
chloride, 2-methacryl-N,N,N-trimethylethan-1-aminium chloride,
2-methacryl-N,N-dimethyl-N-ethylethan-1-aminium ethyl sulfate, and
dimethyldiallylammonium chloride.
[0096] The copolymer according to the present disclosure comprises
1% to 40% by weight, preferably 2% to 30%, and especially
preferable from 5 to 20% by weight of the copolymer, of Monomer B.
The weight ratio of Monomer A to Monomer B is preferably equal to
or greater than 2:1, preferably 3:1 to 5:1.
[0097] Monomer C
[0098] As optional components of the copolymer of the present
disclosure, monomers C and D may also be utilized. Monomer C is
selected from anionic monoethylenically unsaturated monomers.
Suitable monomer C may be selected from: [0099] (a)
.alpha.,.beta.-unsaturated monocarboxylic acids which preferably
have 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid,
2-methylenebutanoic acid, crotonic acid and vinylacetic acid,
preference being given to acrylic acid and methacrylic acid; [0100]
(b) unsaturated dicarboxylic acids, which preferably have 4 to 6
carbon atoms, such as itaconic acid and maleic acid, anhydrides
thereof, such as maleic anhydride; [0101] (c) ethylenically
unsaturated sulfonic acids, such as vinylsulfonic acid,
acrylamido-propanesulfonic acid, methallylsulfonic acid,
methacrylsulfonic acid, m- and p-styrenesulfonic acid,
(meth)acrylamidomethanesulfonic acid,
(meth)acrylamidoethanesulfonic acid,
(meth)acrylamidopropanesulfonic acid,
2-(meth)acrylamido-2-methylpropanesulfonic acid,
2-acrylamido-2-butanesulfonic acid, 3-methacryl
amido-2-hydroxypropanesulfonic acid, methanesulfonic acid acrylate,
ethanesulfonic acid acrylate, propanesulfonic acid acrylate,
allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid and
1-allyloxy-2-hydroxypropanesulfonic acid; and [0102] (d)
ethylenically unsaturated phosphonic acids, such as vinylphosphonic
acid and m- and p-styrenephosphonic acid.
[0103] The anionic Monomer C can be present in the form of water
soluble free acids or in water-soluble salt form, especially in the
form of alkali metal and ammonium, in particular alkylammonium,
salts, and preferred salts being the sodium salts.
[0104] A preferred Monomer C may be selected from acrylic acid,
methacrylic acid, maleic acid, vinylsulfonic acid, 2-(meth)
acrylamido-2-methylpropanesulfonic acid and vinylphosphonic acid,
particular preference being given to acrylic acid, methacrylic acid
and 2-acrylamido-2-methylpropanesulfonic acid.
[0105] The proportion of monomer C in the copolymer of the present
disclosure can be up to 15% by weight, preferably from 1% to 5% by
weight of the copolymer.
[0106] If monomer C is present in the copolymer of the present
disclosure, then, the molar ratio of monomer B to monomer C is
greater than 1. The weight ratio of Monomer A to monomer C is
preferably equal to or greater than 4:1, more preferably equal to
or greater than 5:1. Additionally, the weight ratio of monomer B to
monomer C is equal or greater than 2:1, and even more preferable
from 2.5:1
[0107] Monomer D
[0108] As an optional component of the copolymer of the present
disclosure, monomer D may also be utilized. Monomer D is selected
from nonionic monoethylenically unsaturated monomers selected from:
[0109] (a) esters of monoethylenically unsaturated
C.sub.3-C.sub.6-carboxylic acids, especially acrylic acid and
methacrylic acid, with monohydric C.sub.1-C.sub.22-alcohols, in
particular C.sub.1-C.sub.16-alcohols; and hydroxyalkyl esters of
monoethylenically unsaturated C.sub.3-C.sub.6-carboyxlic acids,
especially acrylic acid and methacrylic acid, with divalent
C.sub.2-C.sub.4-alcohols, such as methyl (meth)acrylate, ethyl
(meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate,
tert-butyl (meth)acrylate, ethylhexyl (meth)acrylate, decyl
(meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate,
cetyl (meth)acrylate, palmityl (meth)acrylate and stearyl
(meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl
(meth)acrylate and hydroxybutyl (meth)acrylate; [0110] (b) amides
of monoethylenically unsaturated C.sub.3-C.sub.6-carboxylic acids,
especially acrylic acid and methacrylic acid, with
C.sub.1-C.sub.12-alkylamines and di(C.sub.1-C.sub.4-alkyl)amines,
such as N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide,
N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide,
N-tert-butyl(meth)acrylamide, N-tert-octyl(meth)acrylamide and
N-undecyl(meth)acrylamide, and (meth)acrylamide; [0111] (c) vinyl
esters of saturated C.sub.2-C.sub.30-carboxylic acids, in
particular C.sub.2-C.sub.14-carboxylic acids, such as vinyl
acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate
and vinyl laurate; [0112] (d) vinyl C.sub.1-C.sub.30-alkyl ethers,
in particular vinyl C.sub.1-C.sub.18-alkyl ethers, such as vinyl
methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl
isopropyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl
2-ethylhexyl ether and vinyl octadecyl ether; [0113] (e)
N-vinylamides and N-vinyllactams, such as N-vinylformamide,
N-vinyl-N-methyl-formamide, N-vinylacetamide,
N-vinyl-N-methylacetamide, N-vinylimidazol, N-vinylpyrrolidone,
N-vinylpiperidone and N-vinylcaprolactam; [0114] (f) aliphatic and
aromatic olefins, such as ethylene, propylene,
C.sub.4-C.sub.24-.alpha.-olefins, in particular
C.sub.4-C.sub.16-.alpha.-olefins, e.g. butylene, isobutylene,
diisobutene, styrene and .alpha.-methylstyrene, and also diolefins
with an active double bond, e.g. butadiene; [0115] (g) unsaturated
nitriles, such as acrylonitrile and methacrylonitrile.
[0116] A preferred monomer D is selected from methyl
(meth)acrylate, ethyl (meth)acrylate, (meth)acrylamide, vinyl
acetate, vinyl propionate, vinyl methyl ether, N-vinylformamide,
N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam.
N-vinylimidazol is particularly preferred.
[0117] If the monomer D is present in the copolymer of the present
disclosure, then the proportion of monomer D may be up to 40%,
preferably from 1% to 30%, more preferably from 5% to 20% by weight
of the copolymer.
[0118] Preferred copolymers of the present disclosure include:
##STR00004##
wherein indices y and z are such that the monomer ratio (z:y) is
from 3:1 to 20:1 and the indices x and z are such that the monomer
ratio (z:x) is from 1.5:1 to 20:1, and the polymer has a weight
average molecular weight of from 20,000 to 500,000 g/mol,
preferably from greater than 25,000 to 150,000 g/mol and especially
from 30,000 to 80,000 g/mol.
[0119] The copolymers according to the present disclosure can be
prepared by free-radical polymerization of the Monomers A and B and
if desired C and/or D. The free-radical polymerization of the
monomers can be carried out in accordance with all known methods,
preference being given to the processes of solution polymerization
and of emulsion polymerization. Suitable polymerization initiators
are compounds which decompose thermally or photochemically
(photoinitiators) to form free radicals, such as benzophenone,
acetophenone, benzoin ether, benzyl dialkyl ketones and derivatives
thereof.
[0120] The polymerization initiators are used according to the
requirements of the material to be polymerized, usually in amounts
of from 0.01% to 15%, preferably 0.5% to 5% by weight based on the
monomers to be polymerized, and can be used individually or in
combination with one another.
[0121] Instead of a quaternized Monomer B, it is also possible to
use the corresponding tertiary amines. In this case, the
quaternization is carried out after the polymerization by reacting
the resulting copolymer with alkylating agents, such as alkyl
halides, dialkyl sulfates and dialkyl carbonates, or benzyl
halides, such as benzyl chloride. Examples of suitable alkylating
agents which may be mentioned are, methyl chloride, bromide and
iodide, ethyl chloride and bromide, dimethyl sulfate, diethyl
sulfate, dimethyl carbonate and diethyl carbonate.
[0122] The anionic monomer C can be used in the polymerization
either in the form of the free acids or in a form partially or
completely neutralized with bases. Specific examples that may be
listed are: sodium hydroxide solution, potassium hydroxide
solution, sodium carbonate, sodium hydrogen carbonate,
ethanolamine, diethanolamine and triethanolamine.
[0123] To limit the molar masses of the copolymers according to the
present disclosure, customary regulators can be added during the
polymerization, e.g. mercapto compounds, such as mercaptoethanol,
thioglycolic acid and sodium disulfite. Suitable amounts of
regulator are 0.1% to 5% by weight based on the monomers to be
polymerized.
[0124] Quaternary Compound
[0125] The liquid hard surface cleaning composition may comprise a
quaternary compound. Preferably, the liquid hard surface cleaning
composition comprises the quaternary compound at a level of from
0.001 to 2% wt %, more preferably from 0.002 to 0.5 wt %, most
preferably from 0.005 wt % to 01 wt % of the composition.
[0126] Traditionally, compositions comprising quaternary compounds
tend to leave unsightly filming and/or streaking on the treated
surfaces. However, compositions as presently disclosed surprisingly
provide improved shine and reduced streaking. Without being bound
to theory this improved shine benefit is a result of the dewetting
property of the solvent. Furthermore, the compositions disclosed
provide high antibacterial benefit delivering 5 logs micro efficacy
while still delivering high shine. In the case of premoisten wipes,
without being bound to theory, the cleaning and shine benefit are
improved when the pad contains cellulose, preferentially between 50
to 200 gsm, more preferentially between 80 to 150 gsm, so that the
negative sites of the cellulose bind some of the quaternary
compounds reducing the expressed or release level of the quaternary
compounds and thereby reducing their negative impacts on cleaning,
shine and haze while maintaining its micro bacterial elimination
efficacy.
[0127] Quaternary compounds useful herein are preferably selected
from the group consisting of C6-C18 alkyltrimethylammonium
chlorides, C6-C18dialkyldimethylammonium chlorides, and mixtures
thereof. Preferably, the quaternary compound is selected from the
group consisting of a C8-C12 alkyltrimethylammonium chloride, a
C8-C12 dialkyldimethylammonium chloride, and mixtures thereof. Most
preferably, the quaternary compound is C10 dialkyldimethylammonium
chloride.
[0128] Non-limiting examples of useful quaternary compounds
include: (1) Maquat.RTM. (available from Mason), and Hyamine.RTM.
(available from Lonza); (2) di(C6-C14)alkyl di short chain (C1-4
alkyl and/or hydroxyalkl) quaternary such as Uniquat.RTM. and
Bardac.RTM. products of Lonza, (3) N-(3-chloroallyl) hexaminium
chlorides such as Dowicil.RTM. and Dowicil.RTM. available from Dow;
and (4) di(C8-C12)dialkyl dimethyl ammonium chloride, such as
didecyldimethylammonium chloride (Bardac 22, Uniquat 2250 or Bardac
2250), and dioctyldimethylammonium chloride (Bardac 2050).
[0129] The quaternary compounds preferably are not benzyl quats. An
example of such benzyl quat includes alkyl dimethyl benzyl ammonium
chloride (Uniquat QAC).
[0130] Nitrogen-Containing Polymer
[0131] The liquid hard surface cleaning composition may comprise a
nitrogen-containing polymer. Nitrogen-containing polymers useful
herein include polymers that contain amines (primary, secondary,
and tertiary), amine-N-oxide, amides, urethanes, and/or quaternary
ammonium groups. When present, it is important that the polymers
herein contain nitrogen-containing groups that tend to strongly
interact with the surface being treated in order to displace any
present cationic quaternary compound from the surface.
[0132] Preferably, the polymers herein contain basic nitrogen
groups. Basic nitrogen groups include primary, secondary, and
tertiary amines capable of acting as proton acceptors. Thus, the
preferred polymers herein can be nonionic or cationic, depending
upon the pH of the solution. Polymers useful herein can include
other functional groups, in addition to nitrogen groups. The
preferred polymers herein are also essentially free of, or free of,
quaternary ammonium groups.
[0133] Preferably, the polymers herein are branched polymers,
especially highly branched polymers including comb, graft,
starburst, and dendritic structures. Preferably, the polymers
herein are not linear polymers.
[0134] The nitrogen-containing polymers herein can be an unmodified
or modified polyamine, especially an unmodified or modified
polyalkyleneimine. Preferably, the nitrogen containing polymers
herein are modified polyamines. Poly (C.sub.2-C.sub.12
alkyleneimines) include simple polyethyleneimines and
polypropyleneimines as well as more complex polymers containing
these polyamines. Polyethyleneimines are common commercial
materials produced by polymerization of aziridine or reaction of
(di)amines with alkylenedichlorides. Polypropyleneimines are also
included herein.
[0135] Although modified polyamines are preferred, linear or
branched polyalkyleneimines, especially polyethyleneimines or
polypropyleneimines, can be suitable in the present compositions to
mitigate filming and/or streaking resulting from such compositions
containing quaternary compounds. Branched polyalkyleneimines are
preferred to linear polyalkyleneimines. Suitable polyalkyleneimines
typically have a molecular weight of from about 1,000 to about
30,000 Daltons, and preferably from about 4,000 to about 25,000
Daltons. Such polyalkyleneimines are free of any ethoxylated and/or
propoxylated groups, as it has been found that ethoxylation or
propoxylation of polyalkyleneimines reduces or eliminates their
ability to mitigate the filming and/or streaking problems caused by
compositions containing quaternary compounds.
[0136] In preferred low-surfactant compositions for use in no-rinse
cleaning methods, such compositions typically comprise
nitrogen-containing polymer at a level of from about 0.005% to
about 1%, preferably from about 0.005% to about 0.3%, and more
preferably from about 0.005% to about 0.1%, by weight of the
composition.
[0137] Examples of preferred modified polyamines useful as
nitrogen-containing polymers herein are branched polyethyleneimines
with a molecular weight of about 25,000 Daltons, and Lupasol.RTM.
SK and Lupasol.RTM. SK(A) available from BASF.
[0138] Additional Polymers
[0139] The liquid hard surface cleaning composition may comprise an
additional polymer. It has been found that the presence of a
specific polymer as described herein, when present, allows further
improving the grease removal performance of the liquid composition
due to the specific sudsing/foaming characteristics they provide to
the composition. Suitable polymers for use herein are disclosed in
co-pending EP patent application EP2272942 (09164872.5) and granted
European patent EP2025743 (07113156.9).
[0140] The polymer can be selected from the group consisting of: a
vinylpyrrolidone homopolymer (PVP); a polyethyleneglycol
dimethylether (DM-PEG); a vinylpyrrolidone/dialkylaminoalkyl
acrylate or methacrylate copolymers; a polystyrenesulphonate
polymer (PSS); a poly vinyl pyridine-N-oxide (PVNO); a
polyvinylpyrrolidone/vinylimidazole copolymer (PVP-VI); a
polyvinylpyrrolidone/polyacrylic acid copolymer (PVP-AA); a
polyvinylpyrrolidone/vinylacetate copolymer (PVP-VA); a polyacrylic
polymer or polyacrylicmaleic copolymer; and a polyacrylic or
polyacrylic maleic phosphono end group copolymer; and mixtures
thereof.
[0141] Typically, the liquid hard surface cleaning composition may
comprise from 0.001% to 1.0% by weight of the total composition of
said polymer, preferably from 0.005% to 0.5%, more preferably from
0.01% to 0.05% and most preferably from 0.01% to 0.03%.
[0142] Fatty Acid
[0143] The liquid hard surface cleaning composition may comprise a
fatty acid as a highly preferred optional ingredient, particularly
as suds supressors. Fatty acids are desired herein as they reduce
the sudsing of the liquid composition when the composition is
rinsed off the surface to which it has been applied.
[0144] Suitable fatty acids include the alkali salts of a
C.sub.8-C.sub.24 fatty acid. Such alkali salts include the metal
fully saturated salts like sodium, potassium and/or lithium salts
as well as the ammonium and/or alkylammonium salts of fatty acids,
preferably the sodium salt. Preferred fatty acids for use herein
contain from 8 to 22, preferably from 8 to 20 and more preferably
from 8 to 18 carbon atoms.
[0145] Suitable fatty acids may be selected from caprylic acid,
capric acid, lauric acid, myristic acid, palmitic acid, stearic
acid, oleic acid, and mixtures of fatty acids suitably hardened,
derived from natural sources such as plant or animal esters (e.g.,
palm oil, olive oil, coconut oil, soybean oil, castor oil, tallow,
ground oil, whale and fish oils and/or babassu oil. For example
coconut fatty acid is commercially available from KLK OLEA under
the name PALMERAB1211.
[0146] Typically, the liquid hard surface cleaning composition may
comprise up to 0.5% by weight of the total composition of said
fatty acid, preferably from 0.05% to 0.3%, more preferably from
0.05% to 0.2% and most preferably from 0.07% to 0.1% by weight of
the total composition of said fatty acid.
[0147] Branched Fatty Alcohol
[0148] The liquid hard surface cleaning composition may comprise a
branched fatty alcohol, particularly as suds suppressors. Suitable
branched fatty alcohols include the 2-alkyl alkanols having an
alkyl chain comprising from 6 to 16, preferably from 7 to 13, more
preferably from 8 to 12, most preferably from 8 to 10 carbon atoms
and a terminal hydroxy group, said alkyl chain being substituted in
the .alpha. position (i.e., position number 2) by an alkyl chain
comprising from 1 to 10, preferably from 2 to 8 and more preferably
4 to 6 carbon atoms. Such suitable compounds are commercially
available, for instance, as the Isofol.RTM. series such as
Isofol.RTM. 12 (2-butyl octanol) or Isofol.RTM. 16 (2-hexyl
decanol) commercially available from Sasol
[0149] Typically, the liquid hard surface cleaning composition may
comprise up to 2.0% by weight of the total composition of said
branched fatty alcohol, preferably from 0.10% to 1.0%, more
preferably from 0.1% to 0.8% and most preferably from 0.1% to
0.5%.
[0150] Perfumes
[0151] The liquid hard surface cleaning compositions preferably
comprise a perfume. Suitable perfumes provide an olfactory
aesthetic benefit and/or mask any "chemical" odor that the product
may have.
[0152] Other Optional Ingredients
[0153] The liquid hard surface cleaning compositions may comprise a
variety of other optional ingredients depending on the technical
benefit aimed for and the surface treated. Suitable optional
ingredients for use herein include builders, other polymers,
buffers, bactericides, hydrotropes, colorants, stabilizers, radical
scavengers, abrasives, soil suspenders, brighteners, anti-dusting
agents, dispersants, dye transfer inhibitors, pigments, silicones
and/or dyes.
[0154] Cleaning Pad
[0155] The liquid hard surface cleaning composition may be used in
combination with a cleaning pad of the present disclosure. The
cleaning pad may be dry and may contact a surface wetted with a
cleaning composition, or the cleaning pad may be pre-moistened. The
cleaning pad may comprise one or more layers.
[0156] Referring to FIGS. 1A, 1B and 2, the cleaning pad 10 may
comprise plural layers, to provide for absorption and storage of
cleaning fluid and other liquids deposited on the target surface.
The target surface will be described herein as a floor, although
one of skill will recognize the invention is not so limited. The
target surface can be any hard surface, such as a table or
countertop, from which it is desired to absorb and retain liquids
such as spill, cleaning solutions, etc.
[0157] The cleaning pad 10 may comprise a liquid pervious floor
sheet 14 which contacts the floor during cleaning and preferably
provides a desired coefficient of friction during cleaning. An
absorbent core 16, preferably comprising an absorbent gelling
material ("AGM") 16A is disposed on, and optionally joined to an
inwardly facing surface of the floor sheet 14. The floor sheet may
have an absorbency of at least 30%, more preferably at least 35%.
It is to be appreciated that if the cleaning pad is to be used to
clean a surface other than a floor, the floor sheet may be the
sheet that contacts the surface to be cleaned.
[0158] The floor sheet of the cleaning pad may have a thickness
from about 1 mm to about 5 mm, more preferably about 1.5 mm to
about 3.0 mm and most preferably about 1.2 mm.
[0159] A smoothing strip 12 may be disposed on the outwardly facing
surface of the floor sheet 14. Optionally, a back sheet 18 may be
joined to the core 16 opposite the floor sheet 14, to provide for
attachment of the cleaning pad 10 to an implement 30. The back
sheet 18 may have an outwardly facing surface with one or more
attachment strips 20 to particularly facilitate attachment to an
implement 30. The cleaning pad 10 may be generally planar and
define an XY plane and associated X, Y axes. The Z axis is
perpendicular thereto and generally vertical when the cleaning pad
10 is in use on a floor.
[0160] If desired, the core 16 may comprise AGM 16A to increase the
absorbent capacity of the cleaning pad 10. The AGM 16A may be in
the form of particles may be distributed within the cleaning pad 10
in such a manner to avoid rapid absorbency and absorb fluids
slowly, to provide for the most effective use of the cleaning pad
10. The AGM 16A also entraps dirty liquid absorbed from the floor,
preventing redeposition. If desired foam absorbent material or
fibrous material may be incorporated into the core 16.
[0161] Examining the cleaning pad 10 in more detail, the cleaning
pad 10 may comprise plural layers disposed in a laminate. The
lowest, or downwardly facing outer layer, may comprise apertures to
allow for transmission of liquid therethrough and to promote the
scrubbing of the target surface. One, two or more cores 16 layers
may provide for storage of the liquids and may comprise the
absorbent gelling materials. The cleaning pad 10 may have an
absorbent capacity of at least 10, 15, or 20 grams of cleaning
solution per gram of dry cleaning pad 10, as set forth in commonly
assigned U.S. Pat. Nos. 6,003,191 and 6,601,261.
[0162] The optional top, or upwardly facing layer, is a back sheet
18, and may be liquid impervious in order to minimize loss of
absorbed fluids and to protect the user's hand if the cleaning pad
10 is used without an implement 30. The top layer may further
provide for releasable attachment of the cleaning pad 10 to a
cleaning implement 30. The top layer may be made of a polyolefinic
film, such as LDPE. A suitable back sheet 18 comprises a PE/PP film
having a basis weight of 10 to 30 gsm.
[0163] The optional top, or upwardly facing layer, is a back sheet
18, and may be liquid impervious in order to minimize loss of
absorbed fluids and to protect the user's hand if the cleaning pad
10 is used without an implement 30. This top layer may also be
pervious to liquid and made of a polyolefinic nonwoven to provide a
soft feel for the user. The top layer may further provide for
releasable attachment of the cleaning pad 10 to a cleaning
implement 30. The impervious top layer may be made of a
polyolefinic film, such as LDPE. A suitable back sheet 18 comprises
a PE/PP film having a basis weight of 10 to 30 gsm. For a liquid
pervious top layer, it may comprise a polyolefinic nonwoven, such
as a PP nonwoven.
[0164] Attached to the back sheet 18 may be one or more optional
attachment strips 20. The attachment strips 20 may comprise
adhesive, preferably pressure sensitive adhesive, or may comprise
loops for removable attachment to complementary hooks on an
implement 30. Suitable loop attachment strips 20 may comprise a
laminate of PE film and Nylon loops.
[0165] The back sheet 18 and floor sheet 14 may be peripherally
joined, as is known in the art. This arrangement creates a pocket
for securely holding the core 16. The core 16 may be juxtaposed
with, and optionally joined to the respective inwardly facing
surfaces of the floor sheet 14 and back sheet 18.
[0166] The core 16 may comprise a single layer or two or more
layers. If plural layers are selected for the core 16, the width of
the layers may decrease as the floor sheet 14 is approached, as
shown. The core 16 may comprise airlaid cellulose and optionally
polymer fiber, as available from Glatfelter of York, Pa. If two
airlaid cellulose core 16 layers are selected, each layer of the
core 16 may have a basis weight of at least about 75, 100, 125,
150, 175, 200, or 225 gsm and less than about 300 gsm.
[0167] Preferably each layer of the core 16 comprises AGM 16A. The
AGM 16A may absorb at least 10, 15 or 20 times its own weight. The
AGM 16A may be blown into the airlaid core 16 layer during
manufacture as is known in the art. Suitable AGM 16A is available
as Z3070G from Evonik of Essen, Germany. Arlaid material containing
a gradient AGM 16A distribution is available from Glatfelter of
York, Pa.
[0168] The gradient distribution AGM 16A may be achieved by using
more than one forming head. For example, an airfelt/AGM 16A line
may have three forming heads. The first head may distribute a
relatively large amount of AGM 16A relative to the cellulose
distributed from that head. The second forming head may distribute
a less amount of AGM 16A relative to the cellulose base, with this
mixture being laid onto top of the first AGM 16A/cellulose base.
This pattern may be repeated using as many forming heads as
desired. If desired the final forming head may distribute pure
cellulose and no AGM 16A. Generally, the layer from each forming
head does not intermix with adjacent layers. Adhesive bonding
and/or thermal bonding may hold superposed layers in place and
provide structural rigidity.
[0169] Suitable core 16 layers and a suitable apparatus and process
for making one or more layers of a core 16 having a gradient AGM
16A distribution are found in U.S. Pat. No. 8,603,622 issued Dec.
10, 2013. The teachings of U.S. Pat. No. 8,603,622 are incorporated
herein by reference at column 5, lines 8-14 for the teaching of a
suitable core 16 layer and at FIGS. 3-4, with the accompanying
discussion at column 16, line 41 to column 17, line 59 for the
teaching of production devices suitable to make a core 16 layer for
the present invention.
[0170] If two airlaid cellulose core 16 layers are selected, the
lower core layer 16L, juxtaposed with the floor sheet 14, may
comprise about 10 to 20 weight percent AGM 16A, with about 15
percent being found suitable. The upper core layer 16U, juxtaposed
with the optional back sheet 18, if any, may comprise about 20 to
about 30 weight percent AGM 16A, with about 25 percent being found
suitable. The total core 16, with all layers thereof considered,
may comprise 5 to 50 w %, or 10 to 45 w % AGM 16A, the amount and
gradient distribution of AGM 16A being found helpful for the
present invention. The percentage of AGM 16A, as described and
claimed herein refers to the weight percentage of AGM 16A in that
particular core 16 layer (16U or 16L), without regard to the floor
sheet 14, back sheet 18, smoothing strip 12 or attachment strips
20.
[0171] Each core layer 16L, 16U and particularly the upper core
layer 16U may be further stratified to provide greater absorbency
benefit. The upper core layer 16U may have three strata, as formed.
The strata may comprise 0, 25, and 50 weight percent, monotonically
increasing as the back sheet 18, if any, is approached, to provide
a gradient distribution.
[0172] Generally, it is desired that the upper core layer 16U
comprise more AGM 16A, on both an absolute basis and a weight
percentage basis than the lower core layer 16L. The arrangement
provides the benefit that gel blocking in the lower core layer 16L
does not prevent full absorption of liquid from the target surface
and that liquids are transported upwardly and away from the floor
sheet 14.
[0173] Any arrangement that provides more AGM 16A, preferably on an
absolute basis or optionally on a weight percentage basis is
suitable. Alternatively, either core 16 layer or a single core 16
layer may have increasing AGM 16A concentration in the Z
direction.
[0174] Any such process, as is known in the art, or arrangement,
which provides for increasing AGM 16A in the Z direction as the
back sheet 18 is approached is herein considered an AGM 16A
gradient. It is to be recognized that the AGM 16A gradient may be
smooth, comprise one or more stepwise increments or any combination
thereof.
[0175] The floor sheet 14 may comprise a discrete apertured
nonwoven having a basis weight of about 20 to about 80 gsm and
particularly about 28 to 60 gsm. The floor sheet 14 may be
hydrophobic and made of synthetic fibers. A suitable floor sheet 14
is a 60 gsm PE/PP discrete apertured spunbond nonwoven available as
SofSpan from Fitsea of Simpsonville, S.C. The floor sheet 14 may
have a contact angle of 101 to 180 degrees with water.
[0176] The floor sheet 14 may comprise a smoothing strip 12. The
smoothing strip 12 may have a width less than the floor sheet 14
and may comprise at least about 10, 20, 30, 40, 50, 60 or 70% of
the floor sheet 14 width. The smoothing strip 12 may have a width
of at least 10, 20, 30, 40, 50, 100, 150, 200, 250, mm and less
than 70, 80, 100, 200 or 300 mm, with a width of 24 to 44 mm being
suitable and a width of 34 mm being preferred.
[0177] The smoothing strip 12 may be hydrophilic. As used herein
hydrophilic means having a contact angle of 0 to 100 degrees, as
measured by the test method set forth herein. The smoothing strip
12 may particularly have a contact angle of 30 to 100 degrees and
more particularly 55 to 90 degrees. The smoothing strip 12 may
comprise at least 50% cellulosic content to be hydrophilic.
[0178] More particularly, a suitable smoothing strip 12 may
comprise a laminate of cellulose fibers and synthetic fibers. Such
a laminate is believed to be helpful in attaining the performance
of the cleaning pads 10 described herein. The cellulose fiber
lamina may be outwardly facing, to provide friction and absorbency
on the floor. The synthetic fiber layer may be positioned on
contacting relationship with the floor sheet 14 to provide
integrity during use.
[0179] A 23 gsm tissue and 17 gsm polypropylene spunbond
hydroentagled, sold as 40 gsm Genesis tissue by Suominen of
Helsinki, Finland has been found to be a suitable smoothing strip
12. Another suitable smoothing strip 12 may comprise 28 gsm tissue
and 17 gsm polypropylene spunbond hydroentagled, sold as 45 gsm
Hydratexture tissue by Suominen.
[0180] The smoothing strip 12 may have a surface texture less than
0.5 mm, 0.4 mm or less than 0.3 mm and even be essentially 0 mm.
Surface texture is measured as the peak to valley distance,
independent of the smoothing strip 12 thickness. A surface texture
of less than 0.5 mm is believed to minimize streaking during
cleaning, particularly when the floor dries and more particularly
when a dark floor dries.
[0181] Wipe
[0182] The cleaning pad may be in the form of a cleaning wipe. The
cleaning wipe may be used as a pre-moistened cleaning wipe or a dry
wipe for use with a cleaning composition.
[0183] If the cleaning wipe is pre-moistened, it is pre-moistened
with a cleaning composition, as described in further detail above,
which provides for cleaning of the target surface, such as a floor,
but yet does not require a post-cleaning rinsing operation.
[0184] The cleaning wipe used in conjunction with this cleaning
composition may comprise natural or synthetic fibers. The fibers
may be hydrophilic, hydrophobic or a combination thereof, provided
that the cleaning wipe is generally absorbent to hold, and express
upon demand, the above described cleaning composition. In one
embodiment, the cleaning wipe may comprise at least 50 weight
percent or at least 70 weight percent cellulose fibers, such as air
laid SSK fibers. If desired, the cleaning wipe may comprise plural
layers to provide for scrubbing, liquid storage, and other
particularized tasks for the cleaning operation. If one or multiple
airlaid cellulose core layers are selected, each layer of the core
16 may have a basis weight of at least about 50, 100, 125, 150,
175, 200, or 225 gsm and less than about 300 gsm. The level of
airlaid cellulose may be important with respect to the retention
and control release of the cleaning solution increasing its mileage
with respect to cleaning performance in pre-moistened wipes and
reducing flooding at the beginning of the cleaning process. In
addition, it may be important formulations that include
antibacterials due to their controlled release of the quaternary
active ingredient.
[0185] A cleaning wipe may have a thickness from about 1 mm to
about 5 mm, more preferably about 1.5 mm to about 3.0 mm and most
preferably about 1.2 mm.
[0186] Optionally, the cleaning wipe may further comprise a
scrubbing strip. A scrubbing strip is a portion of the cleaning
wipe which provides for more aggressive cleaning of the target
surface. A suitable scrubbing strip may comprise a polyolefinic
film, such as LDPE, and have outwardly extending perforations, etc.
The scrubbing strip may be made and used according to commonly
assigned U.S. Pat. Nos. 8,250,700; 8,407,848; D551,409 S and/or
D614,408 S. A suitable pre-moistened cleaning wipe maybe made
according to the teachings of commonly assigned U.S. Pat. Nos.
6,716,805; D614,408; D629,211 and/or D652,633.
[0187] Cleaning Implement
[0188] The cleaning pad 10 and cleaning composition may be used by
hand or with a cleaning implement 30. Referring to FIG. 3, the
cleaning implement 30 may comprise a plastic head 32 for holding
the cleaning pad 10 and an elongate handle 34 connected thereto.
The handle 34 may comprise a metal or plastic tube or solid
rod.
[0189] The head 32 may have a downwardly facing surface, to which
the cleaning pad 10 may be attached. The downwardly facing surface
may be generally flat, or slightly convex. The head 32 may further
have an upwardly facing surface. The upwardly facing surface may
have a universal joint to facilitate connection of the elongate
handle 34 to the head 32.
[0190] A hook and loop system may be used to attach the cleaning
pad 10 directly to the bottom of the head. Alternatively, the
upwardly facing surface may further comprise a mechanism, such as
resilient grippers, for removably attaching the cleaning pad 10 to
the implement 30. If grippers are used with the cleaning implement
30, the grippers may be made according to commonly assigned U.S.
Pat. Nos. 6,305,046; 6,484,346; 6,651,290 and/or D487,173.
[0191] The cleaning implement may further comprise a reservoir for
storage of the cleaning composition, a described in further detail
above. The reservoir may be replaced when the cleaning composition
is depleted and/or refilled as desired. The reservoir may be
disposed on the head or the handle of the cleaning implement of the
reservoir may be separate from the cleaning implement. The neck of
the reservoir may be offset per commonly assigned U.S. Pat. No.
6,390,335. The reservoir may be in the form of a spray bottle.
[0192] The cleaning implement 30 may further comprise a pump for
dispensing cleaning solution from the reservoir onto the target
surface, such as a floor. The pump may be battery powered or
operated by line voltage. Alternatively, the cleaning solution may
be dispensed by gravity flow. The cleaning solution may be sprayed
through one or more nozzles to provide for distribution of the
cleaning solution onto the target surface in an efficacious
pattern.
[0193] If a replaceable reservoir is utilized, the replaceable
reservoir may be inverted to provide for gravity flow of the
cleaning solution. Or the cleaning solution may be pumped to the
dispensing nozzles. The reservoir may be a bottle, and may be made
of plastic, such as a polyolefin. The cleaning implement 30 may
have a sleeve (36), which removably receives the bottle, or other
reservoir. The cleaning implement 30 may have a needle, optionally
disposed in the sleeve (36) to receive the cleaning solution from
the bottle. The bottle may have a needle pierceable membrane,
complementary to the needle, and which is resealed to prevent
undesired dripping of the cleaning solution during insertion and
removal of the replaceable reservoir. Alternatively or
additionally, If desired, the implement 30 may also provide for
steam to be delivered to the cleaning pad 10 and/or to the floor or
other target surface.
[0194] A suitable reservoir of cleaning solution and fitment
therefore may be made according to the teachings of commonly
assigned U.S. Pat. Nos. 6,386,392, 7,172,099; D388,705; D484,804;
D485,178. A suitable cleaning implement 30 may be made according to
the teachings of commonly assigned U.S. Pat. Nos. 5,888,006;
5,960,508; 5,988,920; 6,045,622; 6,101,661; 6,142,750; 6,579,023;
6,601,261; 6,722,806; 6,766,552; D477,701 and/or D487,174. A steam
implement 30 may be made according to the teachings of jointly
assigned 2013/0319463.
[0195] Method of Cleaning a Surface
[0196] Cleaning pads, cleaning wipes, and cleaning implements using
cleaning pads and cleaning wipes may be used along with a liquid
hard surface cleaning composition having an advancing contact
higher than 30.degree. for cleaning hard surfaces.
[0197] Preferably cleaning pads, cleaning wipes, and cleaning
implements using cleaning pads and cleaning wipes may be used along
with a liquid hard surface cleaning composition having from about
0.001 wt % to about 0.015 wt % of an ethoxylated alkoxylated
nonionic surface or a copolymer of the present disclosure and at
least about 93 wt % water are suitable for cleaning household
surfaces.
[0198] More preferably, the liquid hard surface cleaning
composition is used with a cleaning pad having a floor sheet with a
thickness of less than 1.2 mm or a cleaning wipe having a thickness
of less than 1.2 mm. Such combination of cleaning composition and
cleaning pad or cleaning wipe provide improved shine, increased
absorbency and faster drying.
[0199] For general cleaning, especially of floors, a preferred
method of cleaning comprises the steps of:
[0200] wetting a hard surface with a cleaning composition and
removing the cleaning composition from the hard surface by wiping
the hard surface with a cleaning pad or cleaning wipe of the
present disclosure. The step of wetting the hard surface may
involve spraying the hard surface with a liquid hard surface
cleaning composition or contacting the hard surface with a
pre-moistened wipe or cleaning pad to wet the hard surface. A
cleaning implement comprising a pre-moistened or dry cleaning pad
or cleaning wipe may also be used to wet and/or remove the cleaning
composition from the hard surface.
[0201] Test Methods:
[0202] A) Shine Test for Floor Cleaning:
[0203] The shine test is done with soil mixture which consists of a
mixture of consumer relevant soils such as oil, particulates, pet
hair, sugar etc. The dark colored engineered hardwood flooring is
soiled with the soil mixture and cleaned with the liquid hard
surface cleaning composition(s) and a cleaning pad is wiped up and
down for a total of six (6) times to cover the entire flooring,
after letting them dry, results are analyzed by using grading scale
described below.
TABLE-US-00001 and PSU Scale Versus a Reference Grading in absolute
scale: (average of 3 graders): 0 = as new/no streaks and/or film 0
= I see no difference 1 = very slight streaks and/or film 1 = I
think there is difference 2 = slight streaks and/or film 2 = I am
sure there is a slight difference 3 = slight to moderate streaks
and/or film 3 = I am sure there is a difference 4 = moderate
streaks and/or film 4 = I am sure there is a big difference 5 =
moderate/heavy streaks and/or film 6 = heavy streaks and/or
film
[0204] B) Fluid Hysteresis--Advancing minus Receding Contact
Angle
[0205] A contact angle goniometer is used to measure the hysteresis
of the fluid. The method described herein below is derived from
ASTM D5946-09.
[0206] The apparatus for measuring hysteresis and advancing and
receding contact angle has: (1) a liquid dispenser capable of
suspending a sessile drop, as specified, from the tip of the
dispenser, (2) a sample holder that allows a sample to lay flat
without unintended wrinkles or distortions, and hold the sample so
that the surface being measured is horizontal, (3) provision for
bringing the sample and suspended droplet towards each other in a
controlled manner to accomplish droplet transfer onto the test
surface, and (4) means for capturing a profile image of the drop
with minimal distortion. A 5-degree lookdown angle is used, so that
the line of sight is raised 5 degrees from the horizontal and the
baseline of the drop is clearly visible when in contact with the
sample. The apparatus has means for direct angle measurements, such
as image analysis of the drop dimensions and position on the
sample. A FT.ANG.200 dynamic contact angle video system analyzer
manufactured by First Ten Angstroms, Portsmouth, Va. has been found
suitable. FT.ANG. software supplied by First Ten Angstroms (Build
362, Version 2.1) has been found suitable. Lighting is adjusted so
a clear image is resolvable by the software, to extract the
baseline and droplet contour without user input.
[0207] The test liquid shall be kept in clean containers.
[0208] The substrate used for this testing is an engineered,
interlocking tongue and groove planked, hardwood floor with
aluminum oxide polyurethane coating. The floor has a contact angle
measured with deionized water of 100 degrees+/-15 degrees and has a
60 degrees gloss reading of 85+/-5 Gloss Units. A Home Legend
Santos Mahogany Engineered Hardwood floor, UPC 664646301473, has
been found suitable. The area of test sample (i.e., floor sheet or
smoothing strip) is sufficient to prevent spreading of the test
drop to the edge of the sample being tested or drops from
contacting each other. The test surface is not directly touched
during preparation or testing, to avoid finger contamination. The
glossy surface of the floor material is carefully cleaned using an
80/20 deionized water/isopropyl alcohol solution prior to use in
any test.
[0209] The temperature and humidity of the lab must be controlled
to 25.degree. C..+-.2.degree. C. temperature and 40.+-.5% humidity.
Temperature and humidity is recorded during the measurement
process.
[0210] The wooden flooring substrate is placed onto the specimen
holder of the instrument ensuring that the substrate is lying flat
and its glossy surface is facing upwards toward the test fluid
droplet. A single droplet of 6.5+/-1.5 .mu.L of the test fluid is
suspended at the end of a 27 gauge syringe needle. The mounted
substrate sample is brought upward until it touches the pendant
drop. Droplets should not be dropped or squirted onto the substrate
surface. The needle is lowered into the drop until it is at least
0.5 mm from surface. Images of the profile of the drop are
collected at a rate of at least 20 images/s. The test fluid is
slowly pumped at a rate of 1 .mu.L/s until 10 .mu.L has been added
to the drop. This is the advancing contact angle portion of the
test. After waiting 15 seconds, the direction of fluid flow in the
syringe is reversed in order to slowly remove test fluid from the
droplet on the surface of the sample at -1 .mu.L/s until 10 .mu.L
has been removed. This is the receding contact angle portion of the
measurement. The flooring substrate is moved, in order to place the
next droplet of the test fluid onto a clean, undisturbed area of
the substrate, preferably at least 25 mm away from any previous
measurements. A total of five contact angle measurements from the
advancing and receding portion of the test are taken on the
substrate sample using the same test fluid.
[0211] The advancing contact angle is extracted from the video
immediately after the diameter of the drop expands as test fluid is
pumped to the surface by addition through the needle. The drop may
glide across the surface. Averaging values during this gliding
portion would constitute an advancing contact angle as long as the
diameter of the drop is expanding. Test fluid must be added to the
drop at 1 .mu.L/s until the diameter increases. Immediately after
the expansion in diameter, the contact angle is obtained as an
advancing contact angle.
[0212] The advancing contact angle of the test fluid is reported as
the average advancing contact angle of the five measurements.
[0213] The receding contact angle is extracted from the video
immediately after the diameter of the drop contracts as test fluid
is removed from the surface through the needle. Averaging values
during this gliding portion would constitute a receding contact
angle as long as the diameter of the drop is contracting. Test
fluid must be removed from the drop at 1 .mu.L/s until the diameter
decreases. Immediately after the contraction in diameter, the
contact angle is obtained as a receding contact angle.
[0214] The hysteresis in calculated from the advancing contact
angle minus the receding contact angle and it is reported as the
average hysteresis of the five measurements.
[0215] Hysteresis that is less than at least 30, more preferably
less than at least 20, and most preferably less than 10 is consumer
acceptable. Without being bound to theory, the hysteresis of the
fluid corelates to the size or appearance of streaks or water marks
of the left behind fluid on the cleaned surface. Hysteresis below
10 are hardly noticeable by the consumer's naked eyes and are
deemed as having high level of shine and cleanness.
[0216] C) pH Measurement:
[0217] The pH is measured on the neat composition, at 25.degree.
C., using a Sartarius PT-10P pH meter with gel-filled probe (such
as the Toledo probe, part number 52 000 100), calibrated according
to the instructions manual.
[0218] D) Measurement of Quaternary Compound Express Level:
[0219] The quantification of express level of the Quaternary
Compound is done by High performance liquid chromatography-Charged
Aerosol Detector (HPLC-CAD) using an external calibration curve
determined at known concentration of quaternary compound.
Premoistened pads aged for two weeks are expressed and their
solutions analysed by HPLC-CAD. The signal from the HPLC-CAD is
compare with the calibration curve to determine the expressed or
free unbound concentration of the Quaternary Compound released from
the pre-moistened wipe.
EXAMPLES
TABLE-US-00002 [0220] TABLE 1 Ex 4 Ex 5 Wt % Wt % Diethylene
Ethylene Ex 1 Ex 2 Ex 3 glycol glycol Ex 6 Ex 7 Ex 8 Ex 9 Wt % Wt %
Wt % monohexyl monohexyl Wt % Wt % Wt % Wt % Tripropylene Propylene
Dipropylene ether ether Ethylene Propylene Dipropylene Tripropylene
glycol Glycol glycol (Hexyl (Hexyl glycol glycol glycol glycol
methyl N-butyl N-butyl CARBIT CELLOS phenyl phenyl phenyl phenyl
ether ether Ether OL .TM. OLVE .TM. ether ether ether ether Solvent
(TPM) (PnB) (DPnB) Solvent) Solvent) (EPH) (PPH) DiPPh (TPPH)
Surface 30 27.5 28.4 29.2 27.7 42 38.1 37.7 39 Tension (dyne/cm)
HLB 8.1 6.9 6.8 6.7 6.4 6.4 5.9 5.8 5.5 pH 6.5 6.5 6.5 6.5 6.5 6.5
6.5 6.5 6.5 Minors to 100% to 100% to 100% to 100% to 100% to 100%
to 100% to 100% to 100% and Water Shine 3 2 2 2 1.5 1 0.5 0.5 3.5
Result (absolute) Shine -1.50 -0.50 -0.50 -0.50 Reference 0.50 1.00
1.00 -2.00 Result (PSU) CA 35 25 25 30 30 20 8 10 30 Hysteresis
(Adv-Rec)
[0221] As shown in Table 1, compositions having 0.05 wt. of amine
oxide, 0.01 wt. of polymer Mirapol 300, 0.02 wt. % of Uniquat 2250,
0.5 wt. % of a Propylene glycol n-butyl ether, 0.03% of perfume,
98.5 wt. % water, by weight of the overall composition with 0.4% of
the preferred HLB solvents, provide consumer acceptable hysteresis,
streaks and shine as compared to composition using solvents outside
of the preferred HLB range.
TABLE-US-00003 TABLE 2 Ex 10 Ex 11 Ex 12 Ex 13 Ex 14 Ex 15 Ex 16 Ex
17 Wt % Wt % Wt % Wt % Wt % Wt % Wt % Wt % Solvent PPH 0.9 0.9 0.9
0.9 0.9 0.9 0.9 0.9 Surfactant 0.05 0.05 0.05 0.05 0.05 0.05 0.05
0.05 Amine Oxide MEA 0.0 0.03 0.015 0.01 0.005 0.0 0.0 0.0 Citric
Acid 0.0 0.0 0.0 0.0 0.0 0.03 0.09 0.15 pH 6.5 10 9.5 9.0 8.0 4.5
4.0 3.5 Minors to 100% to 100% to 100% to 100% to 100% to 100% to
100% to 100% and Water Shine 0.5 2.5 1.0 1.0 0.5 0.5 0.5 0.5 Result
(absolute) Shine Reference -2.00 -0.50 -0.50 0.0 0.0 0.0 0.0 Result
(PSU) Contact 8 30 15 10 8 5 5 8 Angle Hysteresis (Adv-Rec)
[0222] As shown in Table 2, compositions with 0.9 of the preferred
solvent Dipropylene glycol phenyl ether having 0.05 wt. of amine
oxide, 0.01 wt. of polymer Mirapol 300, 0.02 wt. % of Uniquat 2250,
0.5 wt. % of a Propylene glycol n-butyl ether, 0.03% of perfume,
98.5 wt. % water, by weight of the overall composition, provide
consumer acceptable hysteresis, streaks and shine when used in a pH
range of 3.5 to 9.5 as compared to composition at pH higher than
10.
TABLE-US-00004 TABLE 3 Ex 18 Ex 19 Ex 20 Ex 21 Ex 22 Ex 23 Ex 24 Ex
25 Ex 26 Wt % Wt % Wt % Wt % Wt % Wt % Wt % Wt % Wt % Solvent PPH
0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Surfactant Amine Oxide 0.05
0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Uniquat 2250 0.02 0.070
0.065 0.073 0.100 0.125 0.140 0.220 0.280 gsm of Pulp 148 0.0 80
111 111 136 148 148 148 in pad pH 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0
5.0 Minors to 100% to 100% to 100% to 100% to 100% to 100% to 100%
to 100% to 100% and Water Uniquat 2250 5 670 200 220 300 320 300
470 650 Express Level (PPM) Micro Fail Pass Pass Pass Pass Pass
Pass Pass Pass Efficacy Shine 0.5 2.5 1.0 0.5 1.0 0.5 0.5 1.0 2.5
Result (absolute) Shine Reference -2.00 -0.50 0.0 -0.50 0.0 0.0
-0.50 -2.00 Result (PSU) CA 8 40 12 8 12 5 8 15 30 Hysteresis
(Adv-Rec)
[0223] As shown in Table 3, pre-moistened wipes with 0.4 of the
preferred solvent Dipropylene glycol phenyl ether and Uniquat 2250
between 700 to 2200 ppm, having 0.05 wt. of amine oxide, 0.02 wt.
of polymer Mirapol 300, 0.5 wt. % of a Propylene glycol n-butyl
ether, and 0.03% of perfume, by weight of the overall composition,
provide consumer acceptable hysteresis, resulting in improved
streaks and shine in addition to micro efficacy benefits when used
in a premoistened pad containing cellulose between 80 to 148 gsm
over a pure synthetic pad or non-cellulose containing pad when the
expressed or release level of Uniquat is between 200 and 600
ppm.
[0224] The dimensions and values disclosed herein are not to be
understood as being strictly limited to the exact numerical values
recited. Instead, unless otherwise specified, each such dimension
is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension
disclosed as "40 mm" is intended to mean "about 40 mm".
[0225] Every document cited herein, including any cross referenced
or related patent or application and any patent application or
patent to which this application claims priority or benefit
thereof, is hereby incorporated herein by reference in its entirety
unless expressly excluded or otherwise limited. The citation of any
document is not an admission that it is prior art with respect to
any invention disclosed or claimed herein or that it alone, or in
any combination with any other reference or references, teaches,
suggests or discloses any such invention. Further, to the extent
that any meaning or definition of a term in this document conflicts
with any meaning or definition of the same term in a document
incorporated by reference, the meaning or definition assigned to
that term in this document shall govern.
[0226] While particular embodiments of the present disclosure have
been illustrated and described, it would be obvious to those
skilled in the art that various other changes and modifications can
be made without departing from the spirit and scope of the
invention. It is therefore intended to cover in the appended claims
all such changes and modifications that are within the scope of
this invention.
* * * * *